Huiying Xu; Weijie Chen; Mengyao Bian; Hongtao Xu; Hui Gao; Ting Wang; Zhi Zhou; Wei Yi
ACS Catal. 2021, 11, 14694-14701
https://doi.org/10.1021/acscatal.1c04508

Abstract

Cp*Rh(III)-catalyzed [4 + 3] annulation of N-methoxy amides for the direct assembly of seven-numbered 2H-azepin-2-one frameworks has been realized with gem-difluorocyclopropenes acting as innovative β-monofluorinated three sp2 carbon sources. Either annular arylamides or linear acrylamides with the embedment of various functional groups, including DNA-tagged substrates, were found to be compatible with the established [4 + 3] reaction mode. A redox-neutral Rh(III)–Rh(V)–Rh(III) catalytic cycle, specifically via HOAc-assisted tandem site-/regioselective oxidative addition/reductive elimination/C–F bond cleavage-enabled ring-scission involving the unprecedented olefinic C(sp2)–C(sp2) bond cleavage, has been deduced based on experimental and computational mechanistic studies. Taken together, our findings not only identified gem-difluorocyclopropenes as potent and efficient coupling partners for C–H activation development but also provided a sound basis for the organic integration of transition-metal-catalyzed C–H functionalization with cyclopropene and fluorine chemistries.